Internally plasticizing and crosslinkable monomers and applications thereof

ABSTRACT

Novel compounds derived from traditional semi-drying and non-drying oils featuring internally plasticizing and crosslinkable properties are disclosed and claimed. Preferred embodiments include acrylate or methacrylate esters of hydroxy long-chain olefinic compounds derived from castor oil or lesquerella oil. A process for the preparation of the novel compounds is also disclosed, which involves esterification reaction of ethylenically unsaturated carboxylic acids or its derivatives with substituted hydroxy long-chain olefinic compounds. These compounds are suitable for forming latices, which form films at low minimum film forming temperatures (MFT) ranging from −5 to 10° C. and cure to above ambient glass transition (T g ) polymers without the use of traditional organic cosolvents which contribute to environmental pollution via volatile organic compounds (VOCs) emissions. These latices are therefore useful in waterborne coatings, contact and pressure sensitive adhesives, and inks.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to new compositions of matter which contain anethylenically unsaturated carboxylic ester moiety, and are derived fromtraditional semi-drying and non-drying oils. More particularly, thoughnot exclusively, this invention relates both to novel compositions ofacrylate and methacrylate esters of a long-chain olefinic moiety derivedfrom non-drying oils such as castor oil or lesquerella oil and to aprocess for making these compositions. The invention is also directed tonovel waterborne latex compositions formed from these novel acrylate ormethacrylate compositions having utility in coatings, adhesives and inksto improve and enhance the general application and performanceproperties of these formulations.

2. Description of the Prior Art

Recent Congressional enactments have forced coatings manufacturers todevelop new coating formulations that contain low VOCs yet feature goodperformance properties. However, attempts at developing new formulationsthat contain environmentally acceptable low VOCs have only resulted informulations with poor performance characteristics which are alsoeconomically unattractive.

One problem encountered by the coatings manufacturers is the developmentof formulations containing low VOC-coalescing aids or plasticizers. Forinstance, emulsion polymers are currently formulated with coalescingaids or plasticizers in order to form films at and below ambientconditions yet dry to films of sufficient glass transition temperature(T_(g)) to perform adequately at and above room temperature. In general,the ability of emulsion polymers to form or coalesce into film isgoverned by the minimum film forming temperature (MFT) of the polymer inquestion, which typically approximates T_(g) of that polymer. Thus,there is a dilemma, i.e., low MFT polymers are required in order toexhibit coalescence, flow, and surface wetting properties. However, ifthe polymer remains soft and tacky, the coatings are not usable.Therefore, it is necessary to develop a technology in which coatingformulations contain suitable ingredients with an initial low MFT,followed upon application forms nontacky, durable, hard, and waterresistant surfaces having a Tg significantly above their MFT.

There are few references in literature which describe low MFT coatingcompositions which cure to form high T_(g) films. One such exampleutilizes a terpolymer binder known as Vinamul 3692, which is used insolventless paints. The terpolymer is formed from ethylene, vinylacetate, and acrylated ethylene vinyl acetate. Although the physicalproperties of the paint films are generally good, the latex synthesisinvolves the use of ethylene in high pressure reactors. Such amanufacturing protocol is not available to most latex manufacturers andis not cost effective.

There have been many other reports that disclose coatings compositionsthat cure or dry at ambient conditions into durable products. Forexample, vinylic derivatives of auto-oxidizable drying oils have beensynthesized, which are formulated into crosslinkable emulsioncompositions. However, these emulsion compositions still required theuse of VOCs for film formation and formulation into usable coatings.Moreover, the polymers possessed other drawbacks, i.e., the free radicalpolymerizations of vinyl monomers of high iodine number oils arekinetically unfavorable and the products exhibit moderate to markedincompatibility.

Various other coating compositions which cure under ambient conditionsare known in the prior art. A few such examples involve curing by achemical reaction such as epoxide-carboxylic acid reaction,isocyanate-moisture reaction, polyaziridine-carboxylic acid reaction,and activated methylene-unsaturated acrylic reaction.

There are also literature references which disclose derivatives of fattycompounds suitable in the formation of coatings. For example,acryloxymethyl substituted fatty compounds have been claimed to beuseful in radiation curable coating formulations and as binders in inks.Acrylate esters of castor oil have also been reported to be potentiallyuseful as binders in coatings and other applications.

However, none of these references discloses use of an internallyplasticizing and crosslinkable monomer derived from either a traditionalsemi-drying or a non-drying oil for the formation of coatingformulations. In addition, none of the references discussed aboveutilizes inexpensive and readily available acrylate or otherethylenically unsaturated esters of long-chain olefinic monomers derivedfrom semi- or non-drying oils to form latex or emulsion compositions.Furthermore, none of the references mentioned above describes latex oremulsion compositions featuring low MFTs that cure to above ambientT_(g) without the use of any VOCs and yet featuring enhanced properties.

Therefore, it is an object of this invention to provide novelcompositions having low VOCs and low odor which are suitable for formingcoatings, adhesives, and inks formulations comprising an internallyplasticizing and crosslinkable monomer. An additional objective of thisinvention is to provide a process for the synthesis of the novel latexor emulsion compositions. It is also an objective of this invention toprovide novel internally plasticizing and crosslinkable monomers derived(or obtained) from semi- or non-drying oils, and processes for makingthe same. Yet another objective of this invention is to provide avariety of utilities for these novel compositions. Such utilitiesinclude as a binder in coatings, adhesives, and inks formulationsfeaturing enhanced properties yet contributing zero VOCs. Thecompositions of the present invention have no precedence in the priorart.

3. Prior Art

The following references are disclosed as background art and forinformational purpose.

U.S. Pat. No. 4,626,582 discloses acyloxymethyl fatty compounds whichare useful as monomers in the preparation of radiation curable coatings.

U.S. Pat. No. 4,826,907 discloses an acrylic or methacrylic resinemulsion coating composition, and its use.

U.S. Pat. No. 4,906,684 discloses ambient curing coating compositionswhich are made from aqueous dispersions of copolymers ofacetoacetoxyethyl acrylate or methacrylate, glycidyl acrylate ormethacrylate, and ethylenically unsaturated polymerizable acid and adifferent monomer copolymerizable therewith.

Eur. Pat. Appln. No. 466,409 discloses a polymer blend useful as abinder in an aqueous coating composition containing no coalescent.

Indian Pat. No. 153,599 describes a process for preparing novel vinylmonomers from ricinoleic acid and mixed fatty acids of castor oil.

Indian Pat. No. 154,467 describes a process for the preparation of novelacrylic monomers and polymers from castor oil and methyl ricinoleate.

J. American Oil Chem. Soc., (1966) (pp 542-545) describes synthesis ofacrylate esters of various hydroxy acid derivatives obtainable fromcastor oil.

All of the references described herein are incorporated herein byreference in their entirety.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that coatings, adhesives and inkshaving essentially no VOCs can readily be formed from novel latex oremulsion compositions. In addition, the novel compositions of thepresent invention are comprised of a monomer which features aplasticizing property, and thus serves as an internal plasticizer andsubsequently as a crosslinking agent. The monomers suitable for formingthe latex or emulsion compositions of this invention are derivatives ofsemi- or non-drying oils having an ethylenically unsaturated ester of along-chain olefinic compound. Preferred monomers of this invention areacrylate or methacrylate esters of long-chain olefinic monomers derived(or obtained) from either castor oil or lesquerella oil. The laticesformed by this invention have utility in numerous applications such asin coatings, adhesives, and inks formulations.

Accordingly, the present invention provides a composition having lowvolatile organics content and low odor that is suitable for formingcoatings, adhesives, and inks formulations comprising an aqueousdispersion composed of a blended mixture of

(a) a polymer obtained by the polymerization of:

(i) an internally plasticizing and crosslinkable monomer derived from asemi- or non-drying oil; and

(ii) one or more of ethylenically unsaturated monomers copolymerizabletherewith;

(b) a drier selected from the group consisting of aliphatic carboxylicacid salts of cobalt, manganese, lead, zirconium, calcium, and mixturesthereof, and

(c) a surface-active agent; wherein the total weight percent of thepolymer in said aqueous dispersion is at least from about 5 and not morethan about 80 weight percent, wherein the monomers (i) and (ii) arepresent in the weight ratio ranging from about 1:2 to about 1:99.

In another aspect of the present invention, a process for the formationof a waterborne formulation for coatings, inks or adhesives containing apolymer formed from an ethylenicaly unsaturated ester of a long-chainolefinic compound derived (or obtained) from a semi- or non-drying oilis also provided.

In further aspects of this invention novel monomers suitable for formingthe above mentioned latex or emulsion compositions, and processes formaking these monomers are also provided.

DETAILED DESCRIPTION OF THE INVENTION

Surprisingly, it has now been found that coatings, adhesives and inkshaving essentially no VOCs can readily be formed from novel latex oremulsion compositions. In addition, the novel compositions of thepresent invention are comprised of a monomer which features aplasticizing property, and thus serves as an internal plasticizer. Themonomers suitable for forming the latex or emulsion compositions of thisinvention are derivatives of semi- or non-drying oils having anethylenically unsaturated ester of a long-chain olefinic compound.Preferred monomers of this invention are acrylate or methacrylate estersof long-chain olefinic monomers derived (or obtained) from either castoroil or lesquerella oil. The latices formed by this invention haveutility in numerous applications such as in coatings, adhesives, andinks formulations.

Accordingly, the present invention provides a composition having lowvolatile organic content and low odor that is suitable for formingcoatings, adhesives, and inks formulations comprising an aqueousdispersion composed of a blended mixture of

(a) a polymer obtained by the polymerization of:

(i) an internally plasticizing and crosslinkable monomer derived from asemi- or non-drying oil; and

(ii) one or more of ethylenically unsaturated monomers copolymerizabletherewith;

(b) a drier selected from the group consisting of aliphatic carboxylicacid salts of cobalt, manganese, lead, zirconium, calcium, and mixturesthereof; and

(c) a surface-active agent; wherein the total weight percent of thepolymer in said aqueous dispersion is at least from about 5 and not morethan about 80 weight percent, wherein the monomers (i) and (ii) arepresent in the weight ratio ranging from about 1:2 to about 1:99.

As used herein, the term internally plasticizing monomer is intended tobe generic to a class of compounds wherein the monomers of thisinvention are capable of polymerizing and at the same time act as aplasticizer (i.e., “in-chain” or “internal plasticization”) for thepolymer formed therefrom. Generally, the coatings formulations contain avolatile organic solvent additive(s) that acts as a plasticizer for thepolymeric binder. The role of these volatile organic plasticizers is toreduce the apparent T_(g) of the polymer thereby permitting the coatingto form a useful film at a temperature below the real T_(g) of thepolymer. Thus, by incorporating the internally plasticizing monomers ofthe present invention, the polymers or copolymers formed in thisinvention are self plasticized with no subsequent VOC emissions. As aresult, the compositions of the present invention which are suitable forforming coatings, adhesives, and inks exhibit lower minimum film formingtemperatures (MFTs) than the corresponding T_(g)'s of the curedcompositions.

Additionally, the internally plasticizing monomers of the presentinvention are also capable of crosslinking during the drying process.The term crosslinking used herein is intended to mean that the monomersof the present invention are capable of bonding to itself, and/oranother compound or polymeric chain triggered by a suitable chemical orphysical reaction. In a typical coating formulation, for example, theformulation is first applied onto a desired surface and then cured bysuitable means during which time the crosslinking of the polymericbinder occurs. Thus, the monomers of the present invention may becrosslinked after forming films from the coating compositions. Curingcan be affected by a wide variety of well known techniques in the art.

The internally plasticizing and crosslinkable monomers of the presentinvention are preferably derived from semi- or non-drying oils. The termderived used herein is intended to mean that the monomers of the presentinvention are obtained or formed from a wide variety of semi- ornon-drying oils. Various chemical and physical modifications of thesesemi- or non-drying oils may be made to obtain the desirable monomers ofthe present invention using the methods well known in the art.

Various semi- and non-drying oils may be employed for the formation ofthe monomers of the present invention. The terms semi- and non-dryingoils used herein are defined as those oils which do not show markedincrease in viscosity on exposure to air. Generally, oils are classifiedas drying, semi-drying, or non-drying based on their “iodine value,”that is, the number of grams of iodine required to saturate the doublebonds of 100 grams of an oil. In accordance with this definition, oilshaving an iodine value of about 120 to 150 are generally considered tobe semi-drying oils, and oils having less than 120 are generallyconsidered to be non-drying oils. Illustrative examples of suchsemi-drying oils include safflower oil, sunflower oil, soybean oil, andtobaccoseed oil. Illustrative examples of such non-drying oils includecottonseed oil, coconut oil, rapeseed oil, castor oil, and lesquerellaoil. A detailed description of the classification of various oils may befound in “Surface Coatings—Raw Materials and Their Usage,” Vol. 1,Chapman and Hall, Chapter 4, p-45, (1993), incorporated herein byreference in its entirety.

Accordingly, the preferred internally plasticizing and crosslinkablemonomers derived from semi- or non-drying oils of the present inventionare substituted ethylenically unsaturated carboxylic acid esters oflong-chain olefinic compounds of the formula I:

wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same or differentand are each independently selected from the group consisting of:

hydrogen;

alkoxy group having 1 to 10 carbon atoms;

alkoxyalkyl group having 1 to 10 carbon atoms; and

linear or branched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1;

(b) R₈ is selected from the group consisting of:

—CN,

—COOR;

—CH₂OH,

—CH₂OR;

—CONR′R″; and

—CH₂NR′R″;

where (i) R is selected from the group consisting of:

phenyl and substituted phenyl;

tolyl and substituted tolyl;

benzyl and substituted benzyl;

alkoxyalkyl group having 1 to 10 carbon atoms;

hydroxyalkyl group having 1 to 10 carbon atoms;

acyloxyalkyl group having 1 to 10 carbon atoms;

a linear or branched alkenyl group having 2 to 10 carbon atoms;

linear or branched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and

a multifunctional moiety having the structure II or III:

where R₁₂ and R₁₃ are the same or different and are independentlyselected from the group consisting of:

a substituted or unsubstituted, saturated or unsaturated fatty acidchain;

acrylic and substituted acrylic;

a linear or branched alkyl or alkenyl carboxylic acid moiety having 2 to30 carbon atoms; and

monoalkyl esters of maleic and fumaric acids, where alkyl group contains1 to 4 carbon atoms;

(ii) R′, and R″ are the same or different and are independently selectedfrom the group consisting of:

hydrogen;

phenyl and substituted phenyl;

tolyl and substituted tolyl;

benzyl and substituted benzyl;

alkoxyalkyl group having 1 to 10 carbon atoms;

hydroxyalkyl group having 1 to 10 carbon atoms;

acyloxyalkyl group having 1 to 10 carbon atoms;

a linear or branched alkenyl group having 2 to 10 carbon atoms; and

linear or branched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y),

where n is an integer from 1 to 10, x and y are integers from 0 to 2n+1,and the sum of x and y is 2n+1;

(c) R₉, R₁₀, and R₁₁ are the same or different and are independentlyselected from the group consisting of:

hydrogen;

a carboxylate of the formula —COOR, where R is alkyl group having 1 to10 carbon atoms, or phenyl and substituted phenyl;

phenyl and substituted phenyl;

tolyl and substituted tolyl;

benzyl and substituted benzyl;

a linear or branched alkenyl group having 2 to 10 carbon atoms; and

linear or branched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y),

where n is an integer from 1 to 10, x and y are integers from 0 to 2n+1,and the sum of x and y is 2n+1; and

(d) a, a′, b, b′, and c, are integers, where a and a′ have a value offrom 0 to 10, b and b′ have a value of 0 to 2 with the proviso that sumof b and b′ is 1 or 2, and c has a value of from 0 to 20.

In the above definitions and throughout the present specification,alkoxy means straight or branched chain alkoxy having 1 to 10 carbonatoms, and includes, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy,heptyloxy, octyloxy, nonanyloxy, decanyloxy, 4-methylhexyloxy,2-propylheptyloxy, and 2-ethyloctyloxy.

Alkoxyalkyl means that the alkoxy moiety and the alkyl moiety each arestraight or branched chains having 1 to 10 carbon atoms, and includes,for example, methoxymethyl, ethoxymethyl, propoxymethyl,isopropoxymethyl, butoxymethyl, isobutoxymethyl, tert-butoxymethyl,pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, octyloxymethyl,decyloxymethyl, 2-methoxyethyl, 2-ethyloxyethyl, 2-propoxyethyl,2-butoxyethyl, 2-hexyloxyethyl, 2-octyloxyethyl, 2-nonyloxyethyl,3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-butoxypropyl,3-hexyloxypropyl, 3-octyloxypropyl, 3-decyloxypropyl, 4-methoxybutyl,4-ethoxybutyl, 4-propoxybutyl, 4-butoxybutyl, 4-hexyloxybutyl,4-octyloxybutyl, 4-nonyloxybutyl, 5-methoxypentyl, 5-ethoxypentyl,5-propoxypentyl, 5-butoxypentyl, 5-pentyloxypentyl, 5-hexyloxypentyl,5-octyloxypentyl, 5-decyloxypentyl, 6-methoxyhexyl, 6-ethoxyhexyl,6-propoxyhexyl, 6-butoxyhexyl, 6-pentyloxyhexyl, 6-hexyloxyhexyl,6-octyloxyhexyl, 6-decyloxyhexyl, 8-methoxyoctyl, 8-ethoxyoctyl,8-butoxyoctyl, 8-hexyloxyoctyl, 8-octyloxyoctyl, 10-methoxydecyl,10-propoxydecyl, 10-pentyloxydecyl, and 10-decyloxydecyl.

Hydroxyalkyl means a hydroxy containing straight or branched chain alkylgroup having 1 to 10 carbon atoms, and includes, for example,hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl,2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxy-3-methylpropyl,5-hydroxypentyl, 4-hydroxy-3-methylbutyl, 6-hydroxyhexyl,8-hydroxyoctyl, and 10-hydroxydecyl.

Acyloxyalkyl means that acyloxy moiety and the alkyl moiety each arestraight or branched chains having 1 to 10 carbon atoms, and includes,for example, acetoxymethyl, acryloxymethyl, methacryloxymethyl,propionoxymethyl, acetoxyethyl, acryloxyethyl, butyroxyethyl,acetoxybutyl, acryloxybutyl, hexanoyloxybutyl, acetoxyhexyl,acryloxyhexyl, octanoyloxyhexyl, acetoxyoctyl, acryloxyoctyl,acetoxydecyl, and acryloxydecyl.

Substituted phenyl, tolyl, and benzyl means phenyl, tolyl, or benzylring substituted by at least one suitable substituent group selectedfrom the group consisting of amino, nitro, hydroxy, straight or branchedalkoxy group such as methoxy, straight or branched alkyl and/orfluoroalkyl group such as methyl, trifluoromethyl, alkenyl group such asvinyl, and halogen (fluorine, chlorine, bromine or iodine).

Representative examples of linear or branched alkyl and fluoroalkylgroups having 1 to 10 carbon atoms include, for example, methyl,trifluoromethyl, ethyl, 1,1,2-trifluoroethyl, pentafluoroethyl, propyl,perfluoropropyl, isopropyl, butyl, isobutyl, tert-butyl, perfluorobutyl,1,1,2,3,3-pentafluorobutyl, pentyl, hexyl, heptyl, octyl, nonyl, anddecanyl.

Linear or branched alkenyl means alkenyl moiety having 2 to 10 carbonatoms, and includes, for example, vinyl, 1-propenyl, allyl, isopropenyl,2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 3-nonenyl,and 4-decenyl.

Substituted or unsubstituted, saturated or unsaturated fatty acid chainmeans a variety of long-chain fatty acids present in the oils as one ofthe triglycerides. These fatty acids may further be substituted by oneor more substituents selected from the group consisting of alkyl,alkoxy, alkoxyallcyl, hydroxy, hydroxyalkyl, acyloxyalkyl, and halogensas described hereinabove. Illustrative examples of a few of these fattyacids include oleic acid, elaidic acid, linoleic acid, linolenic acid,erucic acid, brassidic acid, nervonic acid, lauric acid, myristic acid,palmitic acid, margaric acid, stearic acid, arachidic acid, behenicacid, lignoceric acid, cerotic acid, melissic acid and undecylenic acid.

Substituted acrylic means acrylic substituted by at least onesubstituent at the α- or β- position of the acrylic chain. Such asubstituent is selected from the group consisting of methyl, ethyl,propyl, butyl, phenyl, and tolyl. Illustrative examples of substitutedacrylic include methacrylic, ethacrylic, cinnamic, crotonic,isocrotonic, tiglic, and angelic.

A wide variety of linear or branched alkyl or alkenyl carboxylic acidmoieties (as R₁₂ and R₁₃) having 2 to 30 carbon atoms are suitable forforming the internally plasticizing monomers of the present inventioncontaining the multifunctional moiety II or III. Examples of such acidsinclude acetic acid, propionic acid, n-butyric acid, n-hexanoic acid,n-heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauricacid, myristic acid, palmitic acid, margaric acid, stearic acid,arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissicacid and the like. Various other unsaturated fatty and non-fatty acidsincluding the acrylic and substituted acrylics mentioned above may alsobe employed.

Monoalkyl esters of maleic and fumaric acids include, for example,methyl hydrogen maleate, methyl hydrogen fumarate, ethyl hydrogenmaleate, ethyl hydrogen fumarate, propyl hydrogen maleate, propylhydrogen fumarate, butyl hydrogen maleate, and butyl hydrogen fumarate.

Furthermore, and as used herein, the term “substituted” is contemplatedto include all permissible substituents of organic compounds. In a broadaspect, the permissible substituents include acyclic and cyclic,branched and unbranched, carbocyclic and heterocyclic, aromatic andnon-aromatic substituents of organic compounds. Illustrativesubstituents include, for example, those described hereinabove. Thepermissible substituents can be one or more and the same or differentfor appropriate organic compounds. For purposes of this invention, theheteroatoms such as nitrogen may have hydrogen substituents and/or anypermissible substituents of organic compounds described herein whichsatisfy the valencies of the heteroatoms. This invention is not intendedto be limited in any manner by the permissible substituents of organiccompounds.

As mentioned earlier, the preferred internally plasticizing monomers ofthis invention are derived (or obtained) from semi- or non-drying oils;that is, semi- or non-drying oils are subjected to suitable chemical orphysical transformations to obtain these monomers. These startingmaterials may be obtained from natural sources such as vegetable oranimal sources or may be synthetic. Thus, the starting materials whichmay be converted to the desired internally plasticizing monomers of thisinvention contain at least one hydroxy group in their backbone and havea terminal polar moiety (i.e., R_(g) in I) selected from the groupconsisting of —CN, —COOR, —CH₂OH, —CH₂OR, —CONR′R″, and —CH₂NR′R″ whereR, R′, and R″ have the same meaning as defined above. These terminalpolar moieties may be introduced, if necessary, into the compoundsobtained from semi- or non-drying oils using a number of well-knownmethods in the art. A description of a few of such methods may be foundin U.S. Pat. No. 4,356,128 to Rogier, incorporated herein by referencein its entirety.

Briefly, the starting materials containing the terminal group, —COOR maybe obtained by subjecting the oil to suitable transesterificationreaction in the presence of an alcohol ROH. In this instance, the oilwhich is a triglyceride may also be used as such. Triglycerides aretriesters of a glycerol formed by a combination of one or more fattyacids, and thus R in this case is a multifunctional moiety as definedabove (i.e., II or III). The fatty compounds containing —CH₂OH or —CH₂ORterminal groups may be obtained by subjecting the corresponding fattyester to suitable reductive conditions. If necessary, other groupsvulnerable to such reductive conditions may suitably be protected beforesubjecting the fatty ester to reductive conditions.

Similarly, compounds having —CONR′R″ (i.e., amides) may be obtained bythe reaction of corresponding carboxylic acids (or the carboxylic acidhalides such as carboxylic acid chloride) obtained from the oils with anamine, HNR′R″ under suitable reaction conditions. Further subjecting soformed amides to suitable reduction reactions results in the formationof compounds having —CH₂NR′R″ group.

The compounds with the —CN group, for example, may be obtained by firstreacting the fatty acid chlorides with ammonia to form the correspondingamides having the terminal group, —CONH₂. The amides so formed cansubsequently be dehydrated using a number of well-known dehydratingagents known in the art to form the corresponding —CN containingcompounds.

The preferred hydroxy fatty acids that are suitable for forming thelong-chain olefinic ester I may be selected from the group consisting ofricinoleic, lesquerolic, auricolic, and densipolic acid. All of theseacids contain one hydroxy group and at least one double bond in theirback bone. If the starting material employed in the latex or emulsioncompositions of the present invention is a triglyceride, then variousother fatty acids may be employed as R₁₂ and R₁₃ in the triglyceride(i.e., II or III). The preferred fatty acids that may be employed forforming the desired triglycerides may be selected from the groupconsisting of oleic, Einoleic, erucic, and vernolic acid.

However, the fatty acids obtained from the drying oils as such are notsuitable for forming the triglycerides that are suitable as startingmaterials of this invention (i.e., I). In general, fatty acidscontaining more than two double bonds in their back bone are notsuitable starting materials for this invention without furtherderivation as described hereinbelow. Such fatty acids, for example,include linolenic, eleostearic, licanic, and isanic acid. Accordingly,the non-drying oils are generally more preferred in this invention andinclude, for example, cottonseed, coconut, rapeseed, lesquerella,castor, and vernonia oil. The non-drying oils which contain no hydroxygroups in their backbone may be suitably functionalized so as to resultin at least one hydroxy group in their backbone. For example, U.S. Pat.No. 4,626,582 describes synthesis of hydroxymethyl containing fattycompounds; and U.S. Pat. No. 5,312,889 describes formation of a hydroxygroup using an unsaturated fatty compound by epoxidation and reductivering opening, which are incorporated herein by reference in theirentirety. Similarly, drying oils can be suitably transformed intohydroxy fatty acids or their derivatives having an iodine value of 150or less such that they can be used as semi- and/or non-drying oilcomponents of this invention. Particularly preferred non-drying oils arecastor and lesquerella oils.

A wide variety of ethylenically unsaturated carboxylic acids or itsderivatives may be used for the formation of desired starting materialsof the present invention. The carboxylic acids having at least onepolymerizable ethylenic bond per molecule (i.e., a double bond) arepreferred. The acids with an ethylenic bond α,β (i.e., 1,2-) to thecarboxylic group are particularly preferred. Representative examples ofsuch ethylenically unsaturated carboxylic acids include, withoutlimitation, acrylic, methacrylic, maleic, fumaric, itaconic, ethacrylic,crotonic, citraconic, cinnamic, methyl hydrogen fumarate, benzylhydrogen maleate, butyl hydrogen maleate, octyl hydrogen itaconate, anddodecyl hydrogen citraconate. If the acid employed is a dicarboxylicacid, such as maleic acid or fumaric acid, then the resulting startingmaterial is a diester of a desired long-chain olefinic monomer.

The compositions containing the long-chain olefinic monomers of thepresent invention further consists of at least one copolymerizablemonomer. Such a copolymerizable monomer include, broadly, polymerizableacid monomer, a monomer containing at least one ethylenicallyunsaturated polymerizable group, and various other ethylenicallyunsaturated monomers well known in the art.

Polymerizable acid monomers used in this invention are the well knownmono- or polycarboxylic acids which contain one polymerizable bond permolecule. Examples of such acids are acrylic acid, methacrylic acid,maleic acid, fumaric acid, itaconic acid, ethacrylic acid, crotonicacid, citraconic acid, and half esters of the dicarboxylic acids whereinthe esterified alcohol group contains from 1 to about 20 carbon atoms.Examples of suitable half esters are methyl hydrogen maleate, methylhydrogen fumarate, benzyl hydrogen maleate, butyl hydrogen maleate,octyl hydrogen itaconate, dodecyl hydrogen citraconate, and the like.Carboxylic acid anhydrides such as maleic anhydride can also be used.The preferred acids for use in this invention are acrylic andmethacrylic acids.

Copolymerizable monomers that contain at least one ethylenicallyunsaturated polymerizable group referred to hereinabove are any of thewell known monomers which contain at least one ethylenically unsaturatedpolymerizable group per molecule and are copolymerizable with the othermonomers. Examples of such monomers are acrylic and methacrylic esterswherein the ester group contains 1 to about 20 carbon atoms, e.g.,methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, isopropyl acrylate, isopropyl methacrylate, butylacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, decyl acrylate,lauryl methacrylate, benzyl acrylate, and the like. Esters of variousother unsaturated acids include butyl fumarate, octyl fumarate, butylmaleate, and octyl maleate.

Other acrylic or methacrylic esters which can be used in this inventionare multifunctional acrylates or methacrylates, and includes, forexample, propylene glycol monoester of acrylic acid, propylene glycolmonoester of methacrylic acid, ethylene glycol monoester of acrylicacid, ethylene glycol monoester of methacrylic acid, glycidyl acrylate,glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate,and hexanediol diacrylate.

Other copolymerizable monomers are vinyl aromatic monomers, such asstyrene, para-acetoxystyrene, vinyl toluene, alpha methyl styrene, vinylpyridine and the like as well as nitriles and amides, e.g.,acrylonitrile and acrylamide. Other olefinic monomers such as ethylene,propylene, and butadiene are also suitable comonomers for thisinvention.

Additional copolymerizable monomers that can be used in this inventionare the derivatives of the hypothetical vinyl alcohol, i.e., aliphaticvinyl esters such as vinyl formate, vinyl acetate, vinyl propionate,vinyl butyrate, vinyl heptanoate, vinyl pelargonate, vinyl3,6-dioxaheptanoate, vinyl 3,6,9-trioxaundecanoate, the vinyl ester ofversatic acid (sold under the tradename Veova 10™), vinyl esters of neoacids and the like. Other vinyl monomers such as vinyl chloride, vinylsulfonate, vinyl silanes, and vinylidene chloride are also suitablecomonomers.

Various other copolymeriable monomers that impart enhanced properties tothe resulting compositions of the present invention may also be used.One such example is a wet adhesion promoter which improves adhesion ofthe compositions to a wide variety of substances including wood,plastic, and metal surfaces. Illustrative examples of such wet adhesionpromoting monomers include dimethylaminoethyl methacrylate,methacrylamidoethylethyleneurea (sold under the tradename Sipomer® WAMII by Rhone-Poulenc), acrylamidoethylethyleneurea,3-isopropenyl-α,α-dimethylbenzyl isocyanate, and styrene sulfonate.

Any monomers which are copolymerizable with the ethylenicallyunsaturated long-chain olefinic monomer I of this invention can be usedin this invention. Such monomers are those which contain no groups whichare reactive under polymerization conditions with carboxylic acidgroups, —COOR, —CH₂OH, —CH₂OR, p13 CN, —CONR′R″, or —CH₂NR′R″ groups.Thus, suitable comonomers may be employed depending upon the groupspresent in the long-chain olefinic monomer I.

The types and amounts of copolymerizable monomers used in this inventionwill vary depending on the particular end use for which the product ofthis invention is intended. Such variations are well known and can bereadily determined by those skilled in the art. In general, the weightpercents of the internally plasticizing compound, i.e., the long-chainolefinic monomer I and the copolymerizable monomer in the resultingcomposition ranges from about 5 and not more than about 80 weightpercent based upon the total weight of the composition. Preferably, thetotal weight percents range from about 30 to about 70 weight percentbased on the total weight of the composition. The weight ratio of thelong-chain olefinic monomer I to the copolymerizable monomer (s)generally range from about 1:2 to about 1:99, preferably the weightratio range from about 1:7 to about 1:20.

In addition to the polymeric resins formed from the monomer I and thecomonomers mentioned hereinabove, the coatings or adhesives or inkscompositions of the present invention contain at least one drier. Thedriers are materials that promote or accelerate the curing or hardeningof film formers. Typically, driers are used in conjunction with coatingsformulations containing the drying oil components. Surprisingly, it hasnow been found that the metal driers are particularly effective incuring the compositions of the present invention which contain semi- ornon-drying oil components.

The suitable drier is any material which will function as a promoter oran accelerator for the curing or hardening of the film and includes,without limitation, neutral soaps of the formula (R_(x)-COO⁻)₂M²⁺or(R_(x)-COO⁻)₃M³⁺; acid soaps of the formula (R_(x)-COO⁻)₂M²⁺. R_(x)-COOHor (R_(x)-COO⁻ ₃M³⁺. R_(x)-COOH; basic soaps of the formula(R_(x)-COO⁻)₂M²⁺. OH; organic complexed or mixed soaps of the formula(R_(x)-COO⁻) (R′_(x)-COO⁻)M²⁺or(R_(x)-COO⁻(R′_(x)-COO⁻)(R″_(x)-COO⁻)M³⁺; inorganic/organic complexed ormixed soaps of the formula O—M² ⁺-O—CO—R_(x), X—O—M²⁺-O—CO—R_(x), andO—M²⁺-O—CO—R,; where R—COO⁻, R′_(x)-COO⁻and R″_(x)-COO⁻are aliphaticcarboxylic acid ions having 6 to 20 carbon atoms, M=metal ion, andX=phosphorus or boron.

The commonly used carboxylic acids for forming the metal driers arealiphatic acids, preferably fatty acids. Illustrative examples of fattyacids include rosin oil fatty acid, linseed oil fatty acid, and tall oilfatty acid. Various naphthenic acids obtained from certain petroleumcrudes may also be used for forming the suitable metal driers. Thenaphthenic acids generally contains an average of 12-14 carbon atomshaving a cyclopentane nucleus with the carboxyl group terminating a sidechain and with one to three methylenic groups between the carboxyl andthe nucleus. Various other synthetic acids having 8 to 10 carbon atomsare also used to form the metal driers, and include, for example,2-ethylhexanoic acid and neodecanoic acids.

The most commonly used drier metals are cobalt, zirconium, manganese,calcium and lead. Other metals such as zinc, copper, barium, vanadium,cerium, iron, potassium, strontium, aluminum, bismuth, and lithium havealso been used as drier metals. Particularly preferred metal driers arealiphatic carboxylic salts of cobalt, manganese, lead, zirconium,calcium, and mixtures thereof. It has been found that cobalt salts soldunder the tradename Co Hydro-Cure® II are particularly preferred metaldriers for the compositions of the present invention. A detaileddescription of various metal driers may be found in “SurfaceCoatings—Raw Materials and Their Usage,” Vol. I, Chapman & Hall, Chapter33, pp 592-606 (1993), incorporated herein by reference in its entirety.

Although metal driers mentioned hereinabove are particularly effectivein the drying of the films, various other non-metallic driers well-knownin the art may also be employed either as primary driers, auxiliarydriers, or as drier accelerators. Many auxiliary non-metallic driers areeffective in improving the solubility of the active drier metal in thereactive medium or alter the drier metals' redox potential. Examples ofsuch non-metallic driers include 8-hydroxyquinoline, quinoline, salicylaldoxime, pyridine-2-carbaldoxime, acetylacetonate enamines,2-2′-bipyridyl, ethylenediamine, propylenediamine, pyridine,o-vinylpyridine, o-aminopyridine, aniline, o-phenylenediamine,o-toluidine, α-naphthylamine, o-phenanthroline, dipropylamine,diamylamine, acrylonitrile, succinonitrile, o-tolunitrile, o-toluamide,o-tolyl isocyanate, phenyl isocyanate, naphthyl isocyanate, pyrrole,benzimidazole, benzotriazole, and the like. Particularly preferrednon-metallic drier is 2-2′-bipyridyl sold under the tradename DRI-RX™.

As described hereinbelow, the compositions of this invention areprepared by polymerization of monomers emulsified in water usingconventional emulsion polymerization procedures. A suitablesurface-active agent generally known as surfactants are used foremulsification of the monomers. Suitable surfactants include cationic,anionic, amphoteric, or nonionic surfactants or mixtures thereof

Examples of useful anionic surfactants are organosulfates andsulfonates, e.g., sodium and potassium alkyl, aryl, and aralkyl sulfatesand sulfonates, such as sodium 2-ethylhexyl sulfate, potassium2-ethylhexyl sulfate, sodium nonyl sulfate, sodium lauryl sulfate,potassium methylbenzene sulfonate, sodium dodecylbenzene sulfonate,potassium toluene sulfonate and sodium xylene sulfonate; higher fattyalcohols, e.g., stearyl, lauryl, etc., which have been ethoxylated andsulfonated; dialkyl esters of alkali metal sulfosuccinic acid salts,such as sodium diamyl sulfosuccinate, sodium dioxtyl sulfosuccinate, andsodium dioctyl sulfosuccinate, formaldehyde-naphthalene sulfonic acidcondensation products; and alkali metal salts, partial alkali metalsalts and free acids of complex organic phosphate esters.

Examples of useful cationic surfactants include alkylamine salts such aslaurylamine acetate, quaternary ammonium salts such as lauryl trimethylammonium chloride and alkyl benzyl dimethylammonium chlorides, andpolyoxyethylenealkylamines. Examples of the amphoteric surfactants arealkylbetaines such as lauryl-betaine.

Examples of nonionic surfactants which can be used in this invention arepolyethers, e.g., ethylene oxide and propylene oxide condensates whichinclude straight and branched chain alkyl and alkaryl polyethyleneglycol and polypropylene glycol ethers and thioethers;alkylphenoxypoly(ethyleneoxy) ethanols having alkyl groups containingfrom about 7 to about 18 carbon atoms and having from about 4 to about240 ethyleneoxy units, such as heptylphenoxypoly(ethyleneoxy) ethanols,nonylphenoxypoly(ethyleneoxy) ethanols; the polyoxyalkylene derivativesof hexitol including sorbitans, sorbides, mannitans and mannides;partial long-chain fatty acids esters, such as the polyoxyalkylenederivatives of sorbitan monolaurate, sorbitan monopaimitate, sorbitanmonostearate, sorbitan tristearate, sorbitan monooleate and sorbitantrioleate; the condensates of ethylene oxide with a hydrophobic base,said base being formed by condensing propylene oxide with propyleneglycol; sulfur containing condensates, e.g., those prepared bycondensing ethylene oxide with higher alkyl mercaptans, such as nonyl,dodecyl, or tetradecyl mercaptan, or with alkylthiophenols wherein thealkyl group contains from about 6 to about 15 carbon atoms; ethyleneoxide derivatives of long-chain carboxylic acids, such as lauric,myristic, palmitic, or oleic acids or mixtures of acids, such as talloil fatty acids; ethylene oxide derivatives of long-chain alcohols suchas octyl, decyl, lauryl, or cetyl alcohols; and ethylene oxide/propyleneoxide copolymers sold under the tradename Pluoronics™.

A particularly useful surfactant which can be used in this invention isa nonionic surfactant which is an organosilanol derivative of tung oil,or linseed oil, or high erucic acid rapeseed oil. These surfactantcompositions particularly feature high surface activity in formingstable emulsions of organic/water of various difficultly emulsifiablematerials as compared with conventional emulsifying agents. Thesesilanol-based surfactant compositions are described in copending,commonly assigned patent application Ser. No. 08/739,850, filed Oct. 30,1996 U.S. Pat. No. 5,807,922. Another class of preferred surfactants arethose which are copolymerizable with the monomers described hereinabove.

The amounts of surfactants employed in the emulsion polymerizationprocess will range from about 0.01 to about 10 weight percent,preferably about 0.2 to about 5 weight percent based on the total weightof monomers and water.

The compositions of the present invention may contain in addition to thepolymeric resins and metal driers referred to hereinabove, as required,suitable additives such as protective colloids, fillers, coloringagents, antiseptics, biocides, dispersing agents, thickening agents,thixotropic agents, antifreezing agents, and pH adjusting agents.

Examples of protective colloids are partially and fully hydrolyzedpolyvinyl alcohol, hydroxyethyl cellulose, hydroxymethyl cellulose,ethylhydroxyethyl cellulose, carboxymethyl cellulose, ethoxylated starchderivatives, polyacrylic acid, alkali metal polyacrylates,polyacrylamide, poly(methyl vinyl ether/maleic anhydride),polyvinylpyrrolidone, water soluble starch, glue, gelatin, water solublealginates, guar, gum arabic and gum tragacanth. The amounts ofprotective colloids used in the composition varies depending upon theintended application and generally ranges from about 0.1 weight percentto about 2 weight percent based on the total weight of the composition.

Examples of fillers include talc, calcium carbonate, diatomaceous earth,mica, kaolin, barium sulfate, magnesium carbonate, Aerosil, vermiculite,graphite, alumina, silica and rubber powder. Such coloring agents astitanium dioxide and carbon black can also be used as the fillers. Theamount of the filler may be properly selected, and when used, forexample, ranges from about 10 weight percent to about 50 weight percentbased on the total weight of the composition of the present invention.

Various organic pigments and inorganic pigments may be broadly used asthe coloring agents, but non-toxic anticorrosive pigments are preferred.Examples of such pigments are phosphate-type anticorrosive pigments suchas zinc phosphate, calcium phosphate, aluminum phosphate, titaniumphosphate, silicon phosphate, and ortho- and fused phosphates of these;molybdate-type anticorrosive pigments such as zinc molybdate, calciummolybdate, calcium zinc molybdate, potassium zinc molybdate, potassiumzinc phosphomolybdate and potassium calcium phosphomolybdate; andborate-type anticorrosive pigments such as calcium borate, zinc borate,barium borate, barium meta-borate and calcium meta-borate. The amount ofthe coloring agent used may also be properly selected based on theend-use application of the compositions of the present invention.

Examples of the antiseptics are pyrrole compounds, imidazole compounds,thiazole compounds, pyridine compounds and organic halogen compounds.The amount of the antiseptic can be suitably selected, and is, forexample, up to about 4 percent by weight based on the total weight (assolids content) of the composition.

Examples of the biocides, which are used either as wet-state protectors(i.e., in-can protectors) or as film protectors of a coatingcomposition, are a wide variety of bactericides, fungicides oralgicides, and include, without limitation, zinc oxide, cuprous oxide,organotin pigments, copolymers of organotin esters of methacrylic acidwith conventional acrylates, tributyl tin oxide, and mixtures thereof.Other examples of biocides particularly useful as in-can protectors areoxazoladines, organosulfurs, and benzisothiazolins. Any general toxicagent may be suitable as a biocide.

The dispersing agents may, for example, be inorganic dispersing agentssuch as sodium salts of polycarboxylic acids, sodium or ammonium salt offused naphthalene sulfonate, polyoxyalkylene alkyl ethers of phenolether, sorbitan fatty acid esters, polyoxyalkylene fatty acid esters,glycerin fatty acid esters, polyoxyethylene styrene phenol, sodiumtripolyphosphate and sodium hexametaphosphate. As mentioned above, novelorganosilanol derivatives of tung oil, or linseed oil, or high erucicacid rapeseed oil which are useful as surfactants are also suitable asdispersing agents. The amount of the dispersing agent can again beproperly selected depending on the end application of the composition,and may range up to about 10 weight percent based on the total weight ofthe composition.

The thickening and thixotropic agents may be one and the same ordifferent and may be the same as the protective colloids referred tohereinabove. Examples of thickening or thixotropic agents are polyvinylalcohol, cellulose derivatives such as hydroxyethyl cellulose,hydroxypropyl cellulose and carboxymethyl cellulose salt, polyethercompounds, urethane-modified polyether compounds, polycarboxylic acidcompounds, sodium salts of polycarboxylic compounds,polyvinylpyrrolidone, polyoxyethylene derivatives such as polyethyleneglycol ether and polyethylene glycol distearate, sodium alginate andinorganic materials such as sodium silicate and bentonite. The amountsof the thickening or the thixotropic agents can be properly chosendepending upon the type of end-application of the composition of thepresent invention.

Examples of the pH adjusting agents are sodium hydroxide, potassiumhydroxide, sodium hydrogen carbonate, ammonia, triethanolamine, andβ-dimethylaminoethanol. The amount of the pH adjusting agent may be asuitable one which is sufficient to adjust the pH of the composition toa desired value.

Various other additives having functional applications in coatings whichare well known to those skilled in the art may also be used with thecompositions of the present invention. Specific examples of suchfunctional additives are corrosion inhibitors, ultraviolet lightstabilizers, antioxidants, and the like.

Thus, in one of the specific embodiments of this invention the totalsolids content including the internally plasticizing compound, i.e., thelong-chain olefinic monomer I, copolymerizable monomers, and all of thedesirable additives referred to hereinabove is preferably ranging fromabout 30 to about 70 percent by weight based on the total weight of thecomposition.

In another specific embodiment of this invention, the compositionsuitable for forming latex or emulsion coatings comprises an internallyplasticizing compound derived (or obtained) from a non-drying oil havinga substituted ethylenically unsaturated carboxylic acid ester of along-chain olefinic ester of the formula IV.

Where R and R₉ are as defined above, however, preferably R is eithermethyl or multifunctional moieties II or III. Preferred R₉ is eitherhydrogen or methyl, i.e., ethylenically unsaturated ester in thispreferred embodiment is either acrylic or methacrylic ester. a, a′, b,b′, and c, in structure IV are integers, where a and a′ have a value offrom 2 to 4, b and b′ have a value of 0 to 2 with the proviso that sumof b and b′ is 1 or 2, and c has a value of 5 to 12.

The preferred copolymerizable monomers in this embodiment may beselected from the group consisting of vinyl acetate, vinyl chloride,vinyl ester of versatic acid, acrylonitrile, acrylamide, 2-ethylhexylacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate,acrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate,methyl acrylate, and styrene. Various combinations of one or more ofanionic, cationic, amphoteric, or nonionic surfactants may be used inthis embodiment.

The starting materials for the preferred long-chain olefinic ester IV inthe above embodiment is derived (or obtained) from either castor oil orlesquerella oil, or the transesterified product obtained from eithercastor oil or lesquerella oil with methanol. Thus, the long-chainolefinic ester IV may be formed from appropriate starting material bysubjecting it to suitable esterification reaction as described below.

Thus, the preferred starting material for the formation of IV may beselected from the group consisting of castor oil, lesquerella oil,transesterified product of castor oil with methanol, transesterifiedproduct of lesquerella oil with methanol, methyl ricinoleate, and methyllesquerolate. Accordingly, the products formed from these startingmaterials which are the preferred long-chain olefinic esters IV areacrylate ester of methyl ricinoleate, methacrylate ester of methylricinoleate, acrylate ester of methyl lesquerolate, and methacrylateester of methyl lesquerolate.

As stated earlier, by incorporation of the internally plasticizingmonomers (i.e., I or IV) into compositions of the present invention, thecompositions exhibit lower MFTs and cure to resins having T_(g)ssignificantly higher than the MFTs. A further significance of thisinvention is the capability of tailoring the glass transitiontemperature (T_(g)) of the emulsion polymers and the MFTs of thecompositions formed therefrom. The MFTs of a coating composition isdetermined experimentally by using an apparatus described by Protzman etal. in J. Appl. Polymer Sci.. 4, 81 (1960) incorporated herein byreference in its entirety. This apparatus is essentially an aluminumslab in which a constant and uniform temperature gradient may bemaintained. The coating composition to be measured is spread uniformlyin one of several sample wells. The point at which the film becomesdiscontinuous when dry is observed and this temperature is recorded asthe MFT. To ensure that the films are actually continuous when formedabove the MFT, the films are scrapped with a knife edge moving in thedirection from low to high temperature. Below the MFT the material chipsoff the bar easily but above the MFT the coating does not lift off thebar. The transition between easily chipped to strong coating takes placeat the MFT.

Conventional latex polymers generally feature MFTs closer to theirT_(g). Contrary to this conventional norm, the compositions of thepresent invention exhibit MFTs much below the final T_(g) of the curedand crosslinked emulsion polymer contained therein, thus eliminating theneed for a plasticizer which is generally a volatile organic compound(VOC). Particularly, the compositions of the above mentioned preferredembodiment forms film at low MFTs ranging from about −5 to about 10° C.and cures to a resin having a T_(g) higher than 25° C.

The compositions of the present invention are particularly useful ascoatings, adhesives, and inks formulations. A wide variety of coatingformulations may be formed from the compositions of this invention. Ingeneral, the coating compositions are formed by incorporating theemulsion polymers formed from the internally plasticizing compound withone or more of the copolymerizable monomers described hereinabove. Inaddition, the coating compositions contain at least one drier and asurfactant, and as required, one or more of the additives describedhereinabove.

The coatings produced by the cure of the internally plasticizingcompound of this invention are useful in a wide variety of applications,i.e., architectural, decorative, maintenance, or industrial coatings.For example, in the electronics area these materials have applicationsas non-conductive coatings, e.g., solder masks for circuit boards ormoisture resistant coatings for the boards or optical fibers.

Similarly, the compositions of the present invention may be formulatedinto a wide variety of adhesives and inks formulations having a diversevariety of applications. For example, in inks formulations the emulsionpolymers of this invention are useful as binders. In general inkformulation differs from coating formulations in terms of the amounts ofcrosslinking monomers used, i.e., ink formulations generally containhigher amounts of the crosslinker. In addition, ink formulations maycontain higher amounts of driers and drier accelerators for fast dryingof these formulations. Accordingly, an ink formulation containing theemulsion polymers of this invention may be obtained by adding one ormore pigments to the emulsion in accordance with a well-known method.The compositions of this invention may also be employed in formingradiation curable formulations, for example, UV curable high glosscoatings, inks, and adhesives formulations.

An adhesive formulation containing the emulsion polymers of thisinvention may similarly be obtained in accordance with a well -knownmethod. Typically, an adhesive formulation may be formed using theemulsion polymer of this invention in combination with one or more ofsurfactants, protective colloids, and one or more of various otheradditives discussed hereinabove. The adhesive formulations of thisinvention are particularly suitable in the form of emulsion and/oraqueous solution, however, dry-mix, hot-melt, or solutions in organicsolvent can also be formed using the polymers of this invention. Adetailed description of adhesive formulations can be found in “Handbookof Adhesives,” 2nd Ed., edited by I. Skiest, Chapter 28, pp 465-494(1977), Van Nostrand Reinhold Co., incorporated herein by reference inits entirety.

In a further aspect the invention provides a process for the formationof a waterbome formulation for coatings, inks or adhesives containing alatex formed from an ethylenically unsaturated ester of a long-chainolefinic monomer derived from a semi- or non-drying oil comprising thesteps of:

(a) subjecting a substituted long-chain olefinic compound having ahydroxy group to suitable esterification conditions in the presence ofan ethylenically unsaturated carboxylic acid or its suitable derivativefor a sufficient period of time and under suitable conditions oftemperature and pressure to form the corresponding ethylenicallyunsaturated ester of a long-chain olefinic monomer;

(b) subjecting said ester of a long-chain olefinic monomer to suitablepolymerization conditions in the presence of at least one otherethylenically unsaturated copolymerizable monomer for a sufficientperiod of time and under suitable conditions of temperature and pressureto form the corresponding polymer dispersed in an aqueous phase; and

(c) blending said dispersion of said polymer with at least one drierselected from the group consisting of aliphatic carboxylic acid salts ofcobalt, manganese, lead, zirconium, calcium, and mixtures thereof and inthe presence of at least one ionic or non-ionic surface-active agent toform the formulation.

The starting material, i.e., the long-chain olefinic compound V is thesame compound as described hereinabove and is derived (or obtained) froma semi- or non-drying oil.

Where R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈a, a′, b, b′, and c are as definedabove. The preferred starting materials are those having R₈=—COOR andmost preferably derived (or obtained) from the group consisting ofricinoleic, lesquerolic, auricolic, and densipolic acids. These fattyacids are preferably obtained from non-drying oils such as castor oil orlesquerella oil.

The esterification reaction of V and an ethylenically unsaturatedcarboxylic acid or its derivative VI may be carried out using any of thewell-known methods in the art. In the structure VI, R₉, R₁₀, and R₁₁ areas defined above. X is selected from the group consisting of Br, Cl,hydroxy, alkoxy group having 1 to 4 carbon atoms, and acyloxy group sameas the acyloxy group derived from said ethylenically unsaturatedcarboxylic acid or an acyloxy group having 2 to 4 carbon atoms asdescribed hereinabove.

Accordingly, the esterification reaction in the step (a) of the processof the present invention may be generically represented as follows:

In this schematic representation, R′-CO is an acyl group of theethylenically unsaturated carboxylic acid or its derivatives of formulaVI, R″O- refers to the alkoxy group and R′″-COO refers to the acyloxygroup mentioned hereinabove. In most instances the esterificationreaction is carried out by using one mole of the acid or its derivativeVI per mole of hydroxy group present in V. However, it may be desirableto use one of these starting materials in excess of the other in somecases.

The preferred ethylenically unsaturated carboxylic acid and itsderivatives VI are either acrylic or methacrylic derivatives, i.e., R₁₀and R₁₁, are hydrogen and R₉ is either methyl or hydrogen in VI.Accordingly, the preferred acryloyl or methacryloyl compound used toesterify the hydroxy long-chain compound V is a halide such as acryloylchloride, methacryloyl chloride, acryloyl bromide, and methacryloylbromide. Various other acryloyl or methacryloyl derivatives that may beemployed in this esterification reaction include acrylic acid,methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate,ethyl methacrylate, n-propyl acrylate, butyl acrylate, acrylicanhydride, methacrylic anhydride, mixed anhydrides of acrylic and aceticacids, and the like.

The esterification reaction may be carried out with or without anycatalysts. However, in some cases it is preferable to carry out theesterification reaction in the presence of a suitable acid, base ormetal catalysts. Any acid, base or metal catalyst that will function asa catalyst for the esterification conditions may be used in this step(a) of the process of the present invention. Specific examples of suchesterification reactions may be found in U.S. Pat. No. 4,745,213 andU.S. Pat. No. 5,243,069, incorporated herein by reference in theirentirety.

The suitable acid includes, without limitation, mineral acids such asHCl and H₂SO₄; super acids such as hydrofluoric acid, fluorosulfonicacid; organic sulfonic acids such as p-toluene sulfonic acid, methanesulfonic acid, and trifluoromethane sulfonic acid; other inorganic acidssuch as phosphoric acid, and boric acid; carboxylic acids such astrifluoro acetic acid; Lewis acids such as BF₃, AlCl₃, SbF₅, and thelike; and solid acid catalysts such as silica, zeolites, and the like.The suitable base includes an inorganic base such as a metal hydroxide,preferably an alkali metal hydroxide, an alkali metal carbonate, e.g.,K₂CO₃; an alkali metal alkoxide (an ionic organic base), such as NaOCH₃,KOC(CH₃)₃, etc.; an alkali metal organic salt (an ionic organic base)such as potassium acetate, etc.; and an amine (a non-ionic organic base)such as pyridine, or a tri-lower-alkylamine, e.g., tripropylamine,trimethylamine, triethylamine, an hindered base such as2,4-diazabicyclo[2,2,2]octane, etc. Ammonia can also be used as a basein step (a) of the process of the present invention.

Illustrative examples of metal catalysts that are particularly suitablein the transesterification type reactions (i.e., Eq. 2) includederivatives of Group I metals, derivatives of Group IVA metals,derivatives of Group IVB metals, derivatives of manganese and cobalt,and mixtures thereof. These may be preferably lithium acetate, sodiumacetate, potassium acetate, cesium acetate, stannic acid, butylstannoicacid, stannous octanoate, dibutyltin oxide, tin butoxide, dibutyltindiesters, di-n-butyl tin dilaurate, titanium tetrabutoxide, titaniumpropoxide, titanium phenoxide, zirconium butoxide, silicon phenoxide,manganese acetate, cobalt acetate, and mixtures thereof.

The amount of the catalyst employed depends upon the nature of theesterification reaction and the catalyst. Any amount of catalyst thatwould be sufficient to carry out the desired esterification reaction maybe used and may range from about 30 parts per million to one to twomoles of catalyst per mole of the acid or its derivative VI used in thisreaction.

The temperature at which step (a) is conducted ranges from about −10° C.to about 150° C., preferably from about 10° C. to about 100° C. Thepressure in this step (a) is not critical and can be subatmospheric,atmospheric, or super atmospheric.

The reaction times in step (a) will generally range from about 15minutes to about 6 hours or longer and sometimes under an inertatmosphere such as nitrogen.

Using the procedure of step (a) outlined herein, the hydroxy long-chainolefinic compound V undergoes esterification reaction with carboxylicacid or its derivatives VI to form the corresponding ethylenicallyunsaturated ester of a long-chain olefinic monomer I.

In step (b) of the process of the present invention the olefinic monomerI is subjected to suitable emulsion polymerization conditions in thepresence of one or more of suitable copolymerizable monomers having atleast one polymerizable ethylenically unsaturated double bond. Thesuitable copolymerizable monomers of this invention are those which aredescribed hereinabove. The polymerization of these monomers emulsifiedin water can be carried out using conventional emulsion polymerizationprocedures. Typically such polymerization reactions are carried out inthe presence of one or more anionic, cationic, amphoteric, or nonionicsurfactants. The suitable surfactants are those which are describedhereinabove.

The monomers, i.e., the monomer I and the copolymerizable monomers ofthis invention are polymerized by means of a catalytic amount of aconventional free radical polymerization catalyst or catalyst system(which can also be referred to as an addition polymerization catalyst, avinyl polymerization catalyst, or a polymerization initiator),preferably, one which is substantially water soluble. Among suchcatalysts are peroxides, such as hydrogen peroxide, tertiary butylhydroperoxide, cumene hydroperoxide; alkali metal (e.g., sodium,potassium, or lithium), and ammonia persulfates, perphosphates, andperborates; azo nitrites, such as α,α-azobisisobutyronitrile, and watersoluble azo initiators, such as WAKO™ initiators; and redox systemincluding such combinations as mixtures of hydrogen peroxide, t-butylhydroperoxide or the like, and any of the iron salts, titanous salts,zinc formaldehyde sulfoxylate, or sodium formaldehyde sulfoxylate;alkali metal or ammonium persulfate, perborate, or perchlorate togetherwith an alkali metal bisulfite, such as sodium metabisulfite; and alkalimetal persulfate together with an aryl phosphinic acid such as benzenephosphinic acid and the like.

The temperature at which step (b) is conducted ranges from about 10° C.to about 90° C., preferably from about 20° C. to about 75° C. Thepressure in this step (b) is not critical and can be subatmospheric,atmospheric, or super atmospheric.

The reaction times in step (b) will generally range from about 1 hour toabout 6 hours or longer and sometimes under an inert atmosphere such asnitrogen.

Using the procedure of step (b) outlined herein, the ethylenicallyunsaturated ester of a long-chain olefinic monomer I undergoespolymerization reaction with one or more of copolymerizable monomers toform the polymers dispersed in water.

In step (c) of the process of this invention the polymer so formed instep (fb) still dispersed in water is further blended with at least oneor more of a metal drier, surfactant, and desired combinations of theadditives to form the waterborne formulations suitable for use incoatings, adhesives or inks applications. For instance, the suitablemetal driers, surfactants, and various additives are those describedhereinabove. The amounts of these components used depend on the intendeduse of the formulation and generally range in amounts as describedhereinabove.

The blending in step (c) can be carried out in any of themixing/blending devices generally known in the art. The temperature atwhich the blending is conducted is generally around ambient conditions,and ranges from about 10° C. to about 40° C. The reaction times forblending generally range from about 10 minutes to about 60 minutes andsometimes under an inert atmosphere such as nitrogen.

Thus, in one of the preferred embodiments of this invention a processfor the preparation of a coating composition using the internallyplasticizing compound IV is also provided. Using the process of thisinvention described hereinabove the coating composition is prepared inthis embodiment utilizing the compound IV. Accordingly, the compound IVis first prepared employing a corresponding hydroxy fatty acid ester anda substituted or unsubstituted acrylic acid or its derivatives usingappropriate esterification conditions discussed hereinabove. Thecompound IV is then polymerized with one or more of copolymerizablemonomers using an emulsion polymerization conditions, and in the finalstep blended with one or more of driers and other desirable additives toform the coating composition.

In yet another aspect the invention provides novel compounds suitable asinternally plasticizing monomers of this invention for forming the novellatex or emulsion compositions described hereinabove. These monomers aresubstituted ethylenically unsaturated carboxylic acid esters oflong-chain olefinic compounds of the formula Ia:

Where R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₉, R₁₀, R₁₁, a, b, and c are asdefined above. R₈ is selected from the group consisting of —CN,—CONR′R″, and —CH₂NR′R″, —CH₂OH, —CH₂OR, where R, R′, and R″ are asdefined above. The preferred monomers are unsubstituted wherein R₁, R₂,R₃, R₄, R₅, R₆, R₇ are hydrogen and are derived from fatty acidsobtained from semi- or non-drying oils such as castor oil andlesquerella oil. The preferred R₁₀ and R₁₁ groups are also hydrogen, andthe preferred R₉ may be either hydrogen or methyl.

In still another aspect, the invention provides a process for thepreparation of novel monomers Ia using precursor hydroxy long-chaincompounds. The preparation involves an esterification reaction of asuitable hydroxy long-chain compound with an ethylenically unsaturatedcarboxylic acid or its derivatives VI to form the corresponding esterIa. This esterification reaction is identical to the one described abovein step (a) of the process for making the waterborne formulations ofthis invention.

In yet an additional aspect the invention provides another class ofnovel compounds suitable as internally plasticizing monomers of thisinvention for forming the novel latex or emulsion compositions describedhereinabove. These monomers are substituted ethylenically unsaturatedcarboxylic acid esters of long-chain olefinic compounds of the formulaIb:

Where R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₉, R₁₀, R₁₁, a, a′, b, b′, and c areas defined above. R is selected from the group consisting of:

phenyl and substituted phenyl;

tolyl and substituted tolyl;

benzyl and substituted benzyl;

alkoxyalkyl group having 1 to 10 carbon atoms;

hydroxyalkyl group having 1 to 10 carbon atoms,

acyloxyalkyl group having 1 to 10 carbon atoms;

a linear or branched alkenyl group having 2 to 10 carbon atoms;

linear or branched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y),

where n is an integer from 2 to 10, x and y are integers from 0 to 2n+1,and the sum of x and y is 2n+1; and

a multifunctional moiety having the structure II or III:

where R₁₂ and R₁₃ are the same or different and are independentlyselected from the group consisting of:

a substituted or unsubstituted, saturated or unsaturated fatty acidchain;

acrylic and substituted acrylic;

a linear or branched alkyl or alkenyl carboxylic acid moiety having 2 to30 carbon atoms; and

monoalkyl esters of maleic and fumaric acids, where alkyl group contains1 to 4 carbon atoms

The preferred monomers are unsubstituted wherein R₁, R₂, R₃, R₄, R₅, R₆,R₇ are hydrogen and are derived from fatty acids obtained from semi- ornon-drying oils such as castor oil and lesquerella oil. The preferredR₁₀ and R₁₁, groups are also hydrogen, and the preferred R₉ may beeither hydrogen or methyl.

In yet a further aspect the invention provides a process for thepreparation of novel monomers Ib using a precursor hydroxy long-chaincompounds. The preparation involves an esterification reaction of asuitable hydroxy long-chain compound with an ethylenically unsaturatedcaroxylic acid or its derivatives VI to form the corresponding ester Ib.This esterification reaction is identical to the one described above instep (a) of the process for making the waterborne formulations of thisinvention. However, if the starting material Ib contains a hydroxyalkylgroup as a substituent on its ester group, i.e., when R=hydroxyalkylgroup, the esterification may be carried out either using excess of theacid or its derivative VI to form a monomer containing the diester ofethylenically unsaturated acid VI, or the hydroxy group is suitablyprotected to form the monoester as described hereinabove.

As mentioned hereinabove, the compositions of this invention haveutility in a diverse variety of applications. For instance, thecompositions of this invention can be converted to redispersible latexpowder by physical drying of the latex composition. The compositions ofthis invention can also be used to form solvent-free coatings such asadhesives, including pressure sensitive and contact adhesives, which canbe used either at ambient or elevated temperatures. The inks or coatingsformulations formed from the compositions of this invention may be inthe form of waterborne latex or may be in the form of 100% solids. Asignificant advantage of these compositions is that the coatings, inks,and adhesives formed from these compositions are essentially solvent andVOCs free formulations, thus eliminating environmental pollution yetfeaturing enhanced properties.

This invention is further illustrated by the following examples whichare provided for illustration purposes and in no way limit the scope ofthe present invention.

EXAMPLES (GENERAL)

In the Examples that follow, the following abbreviations are used:

MECO - Methacrylated castor oil

ACO - Acrylated castor oil

MECOME - Methacrylated methyl ricinoleate

ACOME - Acrylated methyl ricinoleate

MELO - Methacrylated lesquerella oil

ALO - Acrylated lesquerella oil

ALOME - Acrylated methyl lesquerolate

T_(g) - Glass transition temperature.

NMR - Nuclear magnetic resonance spectroscopy, usually of either proton,¹H; and/or carbon 13, ¹³C nuclei.

IR - Infrared spectroscopy.

DSC - Differential Scanning Calorimetry.

MFT - Minimum film forming temperature.

PVC - Pigment volume concentration.

VOC - Volatile organic content

General Analytical Techniques Used for the Characterization:

A variety of analytical techniques were used to characterize variousstarting materials and the compositions of this invention which includedthe following:

NMR: ¹H and ¹³C NMR spectra were recorded on a Bruker AX-200 MHzspectrometer with 5 mm probes at 200 and 50 MHz, respectively.

DSC: A Mettler DSC-30 was used to determine the T_(g) of the films (midpoint value). The heating rate was maintained at 10° C./minute,generally, over a temperature range of −50° C. to 100° C. The flow rateof nitrogen or air is maintained at 20 mL/min.

MFT: MFT of latexes were determined by a MFFT Bar 90 equipment fromByk-Gardner in accordance with ASTM procedure No. D-2354.

Particle Size Determination: Particle size was measured by a Coulter N4MD sub-micron particle size analyzer.

Tensile Strength Measurements: The tensile strength and percentelongation of the films were determined with a 810 Material Test Systemaccording to ASTM D-2370. The specimen were cut to a width of 13 mm, athickness of 0.06-0.12 mm, and a gauge length of 15 mm. In most cases,the data reported represents an average of 8 measurements.

Measurements of Adhesion and Hardness: The clear latex film adhesion ondiffering substrates was measured in accordance with ASTM procedure No.D-3359. The latex hardness development was monitored in accordance withASTM procedure No. D-3363.

Gel Content and Swelling Index: The extent of film cure was determinedfollowing the method described in U.S. Pat. No. 4,906,684 with minormodifications. The films that were air-dried for two weeks, and removedfrom the substrate were tested as follows: (1) About 2 grams samples offilms were weighed into glass bottles containing 75 mL of toluene, thebottles were capped and shaken constantly, (2) after 3 days, the bottlecontents were decanted onto a weighed fluorocarbon mesh screen (70micron meter mesh opening), and washed with toluene; (3) the mesh screenwas weighed, then dried in a vacuum oven until constant weight wasobtained; and (4) after determining the weight of wet gel and dry gel,the gel content and swelling index were determined according to thefollowing equations:

% Gel Content=(weight of dry gel×100)/weight of film

Swelling Index=(weight of wet gel−weight of dry gel)/weight of dry gel

Dry time: The dry time measurements of the film samples of the coatingscompositions were measured in accordance with ASTM procedure No. D-1640.

Conical mandrel (⅛″) measurements on the film samples were madeaccording to ASTM D-522.

Scrub test was performed in accordance with ASTM procedure No. D-2486.

Sheen and Gloss of the film samples were measured according to ASTMD-523.

Contrast ratio was measured according to D-3022.

Example A

Castor oil was transesterified to methyl ricinoleate using the followingprocedure: 200 grams of castor oil was refluxed with 300 grams ofmethanol and 12 grams of sodium methoxide for 1 hour. After removing thesolvent in vacuo, the product was extracted using petroleum ether. Upondrying and complete removal of the residual solvent, methyl ricinoleatewas formed in quantitative yields.

Example B

Example A was substantially repeated in Example B with the exceptionthat the reaction was carried out using lesquerella oil instead ofcastor oil as follows. 1000 grams of lesquerella oil was refluxed with1500 grams of methanol and 60 grams of sodium methoxide for 3 hours.After removing the solvent in vacuo, the product was extracted usingpetroleum ether. The product was dried and the solvent was removed.Methyl lesquerolate was present in 53-60% mixed with other methyl estersof fatty acids. Purification of methyl lesquerolate from the mixture ofmethyl esters of fatty acids was performed by vacuum distillation.Several nonhydroxy fractions were distilled at different times in thebeginning and the residue in the distillation flask was checked usingGC-mass spectroscopy. When the residue contained higher than 93% puremethyl lesquerolate, the distillation was stopped and the productisolated (yield, 550 grams).

Example 1

Castor oil (207 g; 0.627 hydroxy equivalent) was placed in a three-neckflask under a blanket of nitrogen. The entire reaction contents werecooled in an ice bath. Methacryloyl chloride (25.6 g; 0.246 molequivalent) dissolved in 75 mL of methylene chloride was added slowly tothe cooled castor oil with vigorous stirring in about 2 hours.Triethylamine (22.5 g; 0.223 mol equivalent) dissolved in 50 mL ofmethylene chloride was subsequently added in about an hour. Afteraddition of triethylamine, the solution was allowed to warm to ambienttemperature and was stirred for another 4 hours in order to complete thereaction. The precipitated triethylammonium chloride was removed byfiltration and the filtrate was washed with brine solution (saturatedNaCl) followed by washings with dil. NaOH and dil. HCl. The organiclayer was dried with anhydrous magnesium sulfate and the solvent wasremoved in vacuo to yield methacrylated castor oil (MECO) in essentiallyquantitative yields. MECO was stabilized from polymerization by additionof approximately 10 ppm hydroquinone. The structure of the product wasverified by ¹H and ¹³C NMR spectroscopy.

Example 2

Example 1 was substantially repeated in Example 2 with the exceptionthat the reaction was carried out using acryloyl chloride and castor oilas follows. About 500 grams of castor oil (1.52 mol hydroxy equivalent)was reacted with 149 grams (1.65 mol equivalent) of acryloyl chloride inthe presence of 223 grams of triethylamine (2.21 mol equivalent). Thereaction was performed using 500 mL of benzene as a solvent. Yield ofacrylated castor oil (ACO) was 462 grams. The product was characterizedby ¹H and ¹³C NMR spectroscopy.

Example 3

Example 1 was substantially repeated in Example 3 with the exceptionthat the reaction was carried out using methacryloyl chloride and methylricinoleate as follows. About 103 grams of methyl ricinoleate (0.312 molhydroxy equivalent) was reacted with 37 grams (0.356 mol equivalent) ofmethacryloyl chloride in the presence of 60 grams of triethylamine(0.594 mol equivalent). The reaction was performed using 200 mL ofmethylene chloride as a solvent. A quantitative yield of methacrylatedmethyl ricinoleate (MECOME) was obtained and was characterized by ¹H and¹³C NMR techniques.

Example 4

Example 1 was substantially repeated in Example 4 with the exceptionthat the reaction was carried out using acryloyl chloride and methylricinoleate as follows. About 140 grams of methyl ricinoleate (0.424 molhydroxy equivalent) was reacted with 37 grams (0.36 mol equivalent) ofacryloyl chloride in the presence of 60 grams of triethylamine (0.59 molequivalent). The reaction was performed using 200 mL of methylenechloride as a solvent. A quantitative yield of acrylated methylricinoleate (ACOME) was obtained and was characterized by ¹H and ¹³C NMRtechniques.

Example 5

Example 1 was substantially repeated in Example 5 with the exceptionthat the reaction was carried out using methacryloyl chloride andlesquerella oil as follows. About 220 grams of lesquerella oil (0.430mol hydroxy equivalent) was reacted with 24.0 grams (0.230 molequivalent) of methacryloyl chloride in the presence of 24.2 grams oftriethylamine (0.239 mol equivalent) and using 300 mL of methylenechloride as a solvent. A quantitative yield of methacrylated lesquerellaoil (MELO) was obtained and was characterized by ¹H and ¹³C NMRtechniques.

Example 6

Example 1 was substantially repeated in Example 6 with the exceptionthat the reaction was carried out using acryloyl chloride andlesquerella oil as follows. About 500 grams of lesquerella oil (0.980mol hydroxy equivalent) was reacted with 97.6 grams (0.1.08 molequivalent) of acryloyl chloride in the presence of 149 grams oftriethylamine (1.48 mol equivalent) and 500 mL of benzene as a solvent.Acrylated lesquerella oil (yield: 519 grams) (ALO) was characterized by¹H and ¹³C NMR techniques.

Example 7

Example 1 was substantially repeated in Example 7 with the exceptionthat the reaction was carried out using acryloyl chloride and methyllesquerolate as follows. About 335 grams of methyl lesquerolate (0.900mol hydroxy equivalent) was reacted with 93.3 grams (83.8 molequivalent) of acryloyl chloride in the presence of 136.6 grams oftriethylamine (1.35 mol equivalent) and 1200 mL of benzene as a solvent.Acrylated methyl lesquerolate(ALOME) (yield, 375.2 grams) wascharacterized by ¹H and ¹³C NMR techniques.

Example 8

This Example 8 illustrates the preparation of a latex containing theinternally plasticizing long-chain olefinic monomer of this invention.To a 1 L reactor kettle equipped with an impeller and charged with 110grams of deionized (DI) water, which had been deoxygenated (DO) forabout half an hour by heating to 80° C. under a nitrogen atmosphere, wasadded polyvinyl alcohol (80 grams of 10% solution) followed by theaddition of 12 grams of IGEPAL CA-897 (octylphenol ethoxylates with 40moles of ethylene oxide units obtained from Rhone-Poulenc), 1.2 grams ofIGEPAL CA-630 (octylphenol ethoxylates with 9 moles of ethylene oxideunits obtained from Rhone-Poulenc), and 0.6 grams of sodium bicarbonate.The contents were maintained at 80° C. under a blanket of nitrogen, andthe preseeding was affected by the addition of ammonium persulfate (0.6grams) and vinyl acetate (40 grams), and increasing the impeller speedto 200 rpm.

After 15 minutes of preseeding a monomer mixture or pre-emulsion (astable pre-emulsion can be obtained by mixing all the desirablemonomers, surfactants and water over a stir plate for few minutes)consisting of 30 grams of MECOME (from Example 3) and 130 grams of vinylacetate was added over a period of 3.5 hours at 75° C. maintaining theimpeller speed at 200 rpm. Additional amounts of ammonium persulfate(0.6 grams) dissolved in 30 grams of DI water was cofed into the reactorover a period of 3.75 hours. After the addition of all of the monomersand initiators, the contents of the reactor were stirred at 150 rpm foran additional period of 2 hours at 80° C. The cooled latex was filteredfrom a cheese cloth or a medium mesh filter and poured into a cleancontainer for further evaluation.

The latex exhibited the following properties: particle size: 190 nm;MFT: −1° C.; pH: 4.6; solid contents: 48%; and T_(g): 18.4° C. (with nodriers added). The film formed from the latex exhibited the followingfilm properties: gel content: 62%; swelling: 20; tensile strength: 330psi; and elongation: 1260%.

Example 9-10

Example 8 was substantially repeated in Examples 9 and 10 with theexception that the latex was prepared using the following amounts ofmaterials in each of these examples:

Example 9 Example 10^(c) 10% Polyvinyl alcohol 40 grams 60 grams IGEPALCA-897 (Rhone Poulenc) 12 grams 12 grams IGEPAL CA-630 (Rhone Poulenc)1.2 grams 1.2 grams NaHCO₃ 0.8 grams 0.8 grams DI, DO water 150 grams140 grams Ammonium persulfate 0.6 grams 0.2 grams Vinyl acetate - forseeding 40 grams — Vinyl acetate - with monomer emulsion 114 grams 147grams MECO^(a) — 16 grams ACOME^(b) 16 grams — Butyl acrylate 30 grams34 grams SIPOMER WAM II (Rhone Poulenc) — 3 grams Ammonium persulfate -initiator feed 0.6 grams 0.8 grams DI, DO water - for initiator feed 30grams 30 grams ^(a)from Example 1; ^(b)from Example 4; ^(c)this latexwas chased by adding 0.5 grams of sodium formaldehyde sulfoxylatediluted in 40 grams of water containing 0.4 grams of sodium bicarbonate.

In both examples, the seeding was done at 80° C. for about 10 minutes,and the polymerization itself was conducted at 72° C. The monomers wereadded during a period of about 3.5 hours at an impeller speed of 200rpm, along with the initiator cofed for about 3.75 hours, and postpolymerized for about 1.5 hours. The latices and the films formed fromthem exhibited the following properties:

Example 9 Example 10 Particle Size 180 nm 190 nm MFT −1° C. 2° C. pH 4.95.1 Solid content 45% 43% T_(g) 17 22 % Gel Content - of film 61 54Swelling - of film 24 18 Tensile strength - of film — 860 psi Tensileelongation - of film — 1060%

Examples 11-13

These examples illustrate the effect of metal driers on the films aftercuring. Example 8 was substantially repeated in Examples 11 to 13 withthe exception that the latex was prepared using the following amounts ofmaterials in each of these examples:

Example 11 Example 12 Example 13 10% Polyvinyl alcohol 81 grams — —IGEPAL CA-897 12.3 grams — — (Rhone Poulenc) Sodium dodecyl- — — 0.5grams benzene sulfonate ABEX 40^(a) — 3.5 grams — RHODOFAC BX-660^(b) —3.5 grams — (Rhone Poulenc) SIPOMER BEM^(c) — 1.2 grams — (RhonePoulenc) NaHCO₃ 0.6 grams 0.6 grams — DI, DO water 100 grams 140 grams50 grams Ammonium persulfate 0.6 grams 0.2 grams 0.1 grams Vinylacetate - for 40 grams 10 grams — seeding Preemulsion monomer mixture:Vinyl acetate - with 107 grams 56 grams 70 grams monomer emulsionInternally plasticizing ALO^(d) ALO^(d) ALOME^(e) monomer 50 grams 8grams 7 grams Blutyl acrylate 34 grams 25 grams 11.5 grams VEOVA 10(Shell) — — 10 grams SIPOMER WAM I 1.5 grams 0.75 grams 0.6 grams (RhonePoulenc) SIPOMER WAM II 1.5 grams 0.75 grams 0.7 grams (Rhone Poulenc)Ammonium persul- 0.6 grams 0.4 grams 0.4 grams fate - initiator feedSodium dodecyl- — — 0.5 grams benzene sulfonate IGEPAL CA897 — — 3.5grams (Rhone Poulenc) Sodium carbonate — — 0.4 grams DI, DO water - for30 grams 12 grams 60 grams initiator feed Chaser Solution FeSO₄ — — 0.01grams t-Butyl hydroperoxide — — 0.4 grams Sodium formaldehyde — — 0.3grams sulfoxylate DI water — — 8.5 grams ^(a)an anionic surfactant;^(b)an aromatic phosphate ester with 6 mole of ethylene oxide units;^(c)behenylpolyethoxymethylmethacrylate with 25 mole ethylene oxideunits; ^(d)from Example 6; ^(e)from Example 7.

In all of these examples, the seeding was done at 80° C. for about 10 to15 minutes, and the polymerization itself was conducted at 72° C. Themonomers were added during a period of about 3.5 hours (in about 2 hoursin Example 13) at an impeller speed of 200 rpm, along with initiatorcofed for about 3.75 hours in Example 11, 1.5 hours in Example 12, and2.5 hours in Example 13; and post polymerized for about 2 hours inExamples 11 and 13, and 0.75 hours in Example 12.

The films were formed in these examples with and without the addition ofmetal driers. The samples with metal driers contained 0.08 weightpercent (based on solids) of COBALT HYDROCURE II (obtained from OMG,Inc., Cleveland, Ohio) as a metal drier, 0.5 weight percent (based onsolids) DRI-RX (obtained from OMG, Inc., Cleveland, Ohio) as a drieraccelerator, and I weight percent methyl ethyl ketone peroxide as a freeradical initiator. The latices and the films formed from them exhibitedthe following properties:

Example 11 Example 12 Example 13 Particle Size 200 nm 200 nm 180 nm MFT0° C. 1° C. 0° C. pH 4.9 4.9 4.8 Solid content 48% 42% 50% T_(g) (withno driers added) 20 19 29 T_(g) (after the addition of driers) 39 27 48* *T_(g) of the latex coating

Examples 14-15

Example 8 was substantially repeated in Examples 14 and 15 with theexception that the latex was prepared using the following amounts ofmaterials in each of these examples:

Example 14 Example 15 10% Polyvinyl alcohol 20 grams — IGEPAL CA-897(Rhone Poulenc) 6.3 grams — IGEPAL CA-630 (Rhone Poulenc) 1.2 grams —ABEX 3384 (40% solids) — 3 grams RHODOFAC 13X660 (80% solids) — 3 grams(Rhone Poulenc) SIPOMER cops-I (40% solids)^(a) — 18 grams (RhonePoulenc) Na₂CO₃ 0.4 grams 1 grams DI, DO water 100 grams 120 gramsAmmonium persulfate 0.1 grams 0.05 grams Preemulsion monomer mixture:Styrene - preemulsion addition 47 grams — Internally plasticizingmonomer ACOME^(b) ACOME^(b) 10 grams 8 grams Methyl methacrylate — 40grams Butyl acrylate 42 grams 50 grams Acrylic acid — 1.5 grams SIPOMERWAM I (Rhone Poulenc) 0.75 grams 0.75 grams SIPOMER WAM II (RhonePoulenc) 0.75 grams 0.75 grams IGEPAL CA897 (Rhone Poulenc) 8 grams —SIPOMER cops (Rhone Poulenc) — 18 grams Ammonium persulfate - initiatorfeed 0.4 grams 0.4 grams DI, DO water - for initiator feed 27 grams 7grams Chaser solution FeSO₄ — 0.01 grams t-Butyl hydroperoxide 0.4 grams0.1 grams Sodium formaldehyde sulfoxylate 0.4 grams 0.3 grams DI water 9grams 9 grams ^(a)sodium 1-allyloxy-2-hydroxypropyl sulfonate, obtainedfrom Rhone Poulenc; ^(b)from Example 4.

In both of these examples, the seeding was done at 60° C. for about 10to 15 minutes, and the polymerization itself was conducted at 60° C. Themonomers were added during a period of about 2 hours at an impellerspeed of 200 rpm, along with the initiator cofed for about 2.5 hours,and post polymerized for about 1.5 to 2 hours at 80° C. The latices andthe films formed from them exhibited the following properties:

Example 14 Example 15 Particle Size 160 nm 140 nm MFT −1° C. −4° C. pH4.9 4.3 Solid content 40% 52% T_(g) (with no driers added) 13 — T_(g)(after the addition of drier)  48*  49* *T_(g) of the latex coating

Examples 16 and 17

Examples 16 and 17, illustrate the formation of the Mill Baseformulations used for the preparation of coatings compositions.Specified amounts of the ingredients given below were added to aLightnin mixer at a mixing speed of 800 rpm, and mixed further at 3500rpm for 20 minutes.

Ingredients Example 16 Example 17 TRONOX CR-800 (Kerr McGee) 455 grams1200 grams HUBER 70C (DuPont) 292.5 grams — BEAVERWHITE 325 (ECC) 260grams — DURAMITE (ECC) 325 grams — NATROSOL PLUS (Aqualon) 12 grams 5grams KATHON LX 1.5% (Rohm & Haas) 5 grams 4 grams KTPP (Aldrich) 6.5grams 5 grams BYK 034 (Byk Chemie) 12 grams 9 grams TAMOL 731 25% (Rohm& Haas) 39 grams 30 grams SURFYNOL 465 (Air Products) — 4 grams DI water715 grams 500 grams

Examples 18 and 19

The Examples 18 and 19 illustrate the formation of coatings compositionsusing the polymeric latices of this invention. The latices formed inExamples 9 and 10 were used in these Examples to form the vinyl-acryliclatex coatings compositions. The coatings were pigmented at 55% pigmentvolume concentration (PVC) using the Miff Base formulation of Example16. The ingredients and the respective amounts for forming the coatingscompositions are given below. For comparison, a control experiment,“Control A,” was also carried out using a commercial vinyl-acryliclatex, which had the following properties: MFT:10° C.; T_(g):18° C.; andparticle size: 330 nm. The following coatings compositions were preparedusing a Lightnin mixer set at 200 rpm.

Ingredients Example 18 Example 19 Control A Example 16 - 180 grams 180grams 180 grams Mill Base Formulation DI water 30 grams 22 grams 36grams Na₂CO₃ (20%) 6 grams 7 grams 6 grams BYK 035 (Byk 0.4 grams 0.4grams 0.4 grams Chemie) SURFYNOL 465 (Air 1 gram 1 gram 1 gram Products)Latex Example 9 Example 10 Commercial % solids 45 43 55 Amount 87 grams92 grams 71 grams ROMPAQUE OP - 62 20 grams 20 grams 20 grams LO (36.5%)(Rohm & Haas) POLYPHOBE 107 0.8 grams 1.2 grams 1.3 grams (25%) (UnionCarbide) POLYPHOBE 102 5 grams 6 grams 6.4 grams (25%) (Union Carbide)Butyl cabitol — — 3 grams Propylene glycol — — 7 grams

The coatings of Example 18, 19, and the Control A exhibited thefollowing properties:

Coating Properties Example 18 Example 19 Control A PVC   55% 55%   55%Volume Solids 33.6% 33% 33.5% Weight Solids 49.9% 50% 49.6% StormerViscosity 99 KU 100 KU 105 KU ICI Viscosity 1.6 poise 2 poise 2 poise pH9.1 9.4 8.6 VOC (grams/Liter) <0.4  <0.4  122

Coating films were cast onto Leneta charts, aluminum and steel panels.The dry time for the solventless latex coatings was less than thecontrol, their respective films are significantly harder than those fromthe Control A or other commercial coatings requiring coalescing aids,and adhesion of the solventless coatings of Examples 18 and 19 weresuperior to the coalescent containing Control A. The MFTs of thesolventless coatings of Example 18 and 19 were similar to thoseformulated with the assistance of organic coalescing aids. Comparativeproperties of the films formed from the coating compositions of Examples18 and 19, and the Control A are given below.

Film Properties Example 18 Example 19 Control A Tensile strength 853 psi884 psi 596 psi Elongation at break  8.4%  8.6%  26% Wet thickness 7 mil7 mil 7 mil Volume solids 33.6%   33% 33.5%  Dry time 50 minutes 40minutes 55 minutes MFT 0° C. 0° C. 1° C. Pencil hardness 4H 4H 2HConical mandrel (⅛″) pass pass pass Adhesion on Al 100% 100% 80%Adhesion on steel 100% 100% 80% Scrub test: Initial break 170 160 170Scrub test: Film failure 240 230 250 Sheen, 85° 1.9 1.9 1.7 Contrastratio 95 95 94

Various other coatings compositions at different levels of PVC or solidcontents of the latices can be made using the procedures of Examples 18and 19.

Examples 20 and 21

The Examples 20 and 21 illustrate the formation of solventless coatingscompositions containing the styrene-acrylic Example 14) and all-acryliclatex polymers (Example 15). Examples 18 and 19 were substantiallyrepeated in Examples 20 and 21 with the exception that the Mill Baseformulation of Example 17 was used with the latices of Examples 14 and15. For comparison, two control compositions, Control B and Control C,were also prepared under similar conditions using commercialstyrene-acrylic (MFT: 1° C., particle size: 80 nm, and T_(g): −2° C.)and all-acrylic (MFT:9° C., particle size: 500 nm, and T_(g):14° C.)latices. Specific amounts of the ingredients used for forming thecoatings formulations in Examples 20 and 21, and the respective controlsare given below:

Ingredients Example 20 Control B Example 21 Control A Example 17 - 100grams 100 grams 100 grams 100 grams Mill Base Formulation DI water 35grams 60 grams 35 grams 60 grams Na₂CO₃ (20%) 8.4 grams 8 grams 8.4grams 8 grams BYK 035 (Byk Chemie) 0.4 grams 0.4 grams 0.4 grams 0.4grams SURFYNOL 465 (Air Products) 1.6 gram 1.6 gram 1.6 gram 1.6 gramsLatex Example 14 Commercial Example 15 Commercial % solids - 45 55 45 55Amount 170 grams 138 grams 170 grams 138 grams POLYPHOBE 107 (25%) 1grams 1.3 grams 1 grams 1.3 grams (Union Carbide) POLYPHOBE 102 (25%) 7grams 11 grams 7 grams 11 grams (Union Carbide) Butyl cabitol — 3 grams— 3 grams Propylene glycol — 7 grams — 7 grams

The coatings of Examples 20, 21, and the Controls B and C exhibited thefollowing properties:

Coating Properties Example 20 Control B Example 21 Control C PVC   20%  20%   20%   20% Volume Solids   33% 32.6%   33% 32.6% Weight Solids46.3% 45.6% 46.3% 45.6% Stormer viscosity 82 KU 84 KU 82 KU 84 KU ICI1.2 poise 1.2 poise 1.2 poise 1.2 poise pH 8.2 9.1 8.2 9.1 VOC(grams/Liter) <0.43 118 <0.43 118

The coating films were formed and tested from Examples 20, 21, and theControls B and C following the procedures of Examples 18 and 19.Comparative properties of the films formed from the coating compositionsof Examples 20, 21, and the Controls B and C are given below.

Film Properties Example 20 Control B Example 21 Control C Wet thickness6 mil 6 mil 6 mil — Dry time 50 minutes 70 minutes 55 minutes 60 minutesMFT −2° C. −4° C. −2° C. 6° C. Pencil hardness F 2B F B Conical passpass pass pass mandrel (⅛″) Adhesion on Al 80% 80% 100% 80% Adhesion on80% 80% 100% 80% steel Gloss, 85 89 93 83 82 Gloss, 60 72 75 64 65Gloss, 20° 26 32 20 19 Contrast ratio 97.3 97.2 97.5 97

Example 22

This Example 22 illustrates the use of the internally plasticizingmonomer of this invention directly in an UV curable formulation. An inkformulation was made using the monomer composition of Example 7, ALOMEas follows. Specified amounts of the ingredients as given below wereblended in a Lightnin mixer at 150 rpm for one hour and then to insurethorough mixing the ingredients were transferred to a ball mill andground to a Hegman #7.

Ingredients Parts by weight ALOME, from Example 7 21.4 Fluorescentrocket red AX-135 (Day Glo Color) 1.0 PHOTOMER 3016 (Henkel) 17.0PHOTOMER 4061 (Henkel) 19.0 PHOTOMER 4094 (Henkel) 15.6 PHOTOMER 4149(Henkel) 4.4 PHOTOMER 4770 (Henkel) 5.5 PHOTOMER 6008 (Henkel) 11.2 BYK065 (Byk Chemie) 0.4 BYK 358 (Byk Chemie) 0.3 BYK 325 (Byk Chemie) 0.3IRGACURE 651 (Ciba) 2.7 Benzophenone 1.3

A 2 mil thick film was applied onto wood, aluminums paper and steelpanels with a draw bar, and irradiated under a 600 W medium pressuremercury UV lamp for 4 seconds at a distance of approximately 7″ with aFusion UV curing source to a hard, smooth film. Similar formulations andapplications can be developed using other specialty monomers describedherein.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby, butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A substituted ethylenically unsaturatedcarboxylic acid ester of compound of the formula:

wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same or differentand are each independently selected from the group consisting of:hydrogen; alkoxy group having 1 to 10 carbon atoms; alkoxyalkyl grouphaving 1 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y) where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (b) R₈ is selected from the group consisting of:—CN; —CH₂OR; —CONR′R″; and —CH₂NR′R″; where R, R′, and R″ are the sameor different and are independently selected from the group consistingof: hydrogen; phenyl; tolyl; benzyl; alkoxyalkyl group having 1 to 10carbon atoms; hydroxyalkyl group having 1 to 10 carbon atoms;acyloxyalkyl group having 1 to 10 carbon atoms; a linear or branchedalkenyl group having 2 to 10 carbon atoms; and linear or branched alkyland fluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (c) R₉, R₁₀, and R₁₁ are the same or different andare independently selected from the group consisting of: hydrogen; acarboxylate of the formula —COOR, where R is an alkyl group having 1 to10 carbon atoms, or phenyl; phenyl; tolyl; benzyl; a linear or branchedalkenyl group having 2 to 10 carbon atoms; and linear or branched alkyland fluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; and (d) a, a′, b, b′, and c, are integers, where aand a′ have a value of from 0 to 10, b and b′ have a value of 0 to 2with the proviso that sum of b and b′ is 1 or 2, and c has a value offrom 0 to
 20. 2. The compound as set forth in claim 1 wherein it isderived from a hydroxy fatty acid selected from the group consisting ofricinoleic, lesquerolic, auricolic, and densipolic acid.
 3. The compoundas set forth in claim 1 wherein it is derived from a non-drying oilselected from the group consisting of castor oil and lesquerella oil. 4.The compound as set forth in claim 3 wherein R₉, R₁₀ and R₁₁ arehydrogen.
 5. The compound as set forth in claim 1 wherein saidethylenically unsaturated carboxylic acid ester is derived from acarboxylic acid selected from the group consisting of acrylic,methacrylic, maleic, fumaric, itaconic, ethacrylic, crotonic,citraconic, cinnamic, monomethyl ester of fumaric acid, monobenzyl esterof maleic acid, monobutyl ester of maleic acid, monooctyl ester ofitaconic acid, and monododecyl ester of citraconic acid.
 6. A compoundsuitable for forming latex or emulsion coatings comprising a derivativeof a non-drying oil having an ethylenically unsaturated carboxylic acidester of the formula:

wherein (a) R₈ is selected from the group consisting of: —CN; —CH₂OR;—CONR′R″; and —CH₂NR′R″; where R, R′, and R″ are the same or differentand are independently selected from the group consisting of: hydrogen;phenyl; tolyl; benzyl; alkoxyalkyl group having 1 to 10 carbon atoms;hydroxyalkyl group having 1 to 10 carbon atoms; acyloxyalkyl grouphaving 1 to 10 carbon atoms; a linear or branched alkenyl group having 2to 10 carbon atoms; and linear or branched alkyl and fluoroalkyl groupshaving the formula C_(n)H_(x)F_(y), where n is an integer from 1 to 10,x and y are integers from 0 to 2n+1, and the sum of x and y is 2n+1; (b)R₉ is either hydrogen or methyl; and (c) a, a′, b, b′, and c areintegers, where a and a′ have a value of from 2 to 4, b and b′ have avalue of 0 to 2 with the proviso that sum of b and b′ is 1 or 2, and chas a value of 5 to
 12. 7. The compound as set forth in claim 6 whereinit is derived from either castor oil or lesquerella oil.
 8. A processfor preparing ethylenically unsaturated esters derived from a semi- ornon-drying oil comprising the step of subjecting a compound having ahydroxy group to suitable esterification conditions in the presence ofan ethylenically unsaturated carboxylic acid or its derivative for asufficient period of time and under suitable conditions of temperatureand pressure to form the corresponding ethylenically unsaturated esterof a compound.
 9. The process as set forth in claim 8 wherein saidcompound has the formula:

wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same or differentand are each independently selected from the group consisting of:hydrogen; alkoxy group having 1 to 10 carbon atoms; alkoxyalkyl grouphaving 1 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (b) R₈ is selected from the group consisting of:—CN; —CH₂OR; —CONR′R″; and —CH₂NR′R″, where R, R′, and R″ are the sameor different and are independently selected from the group consistingof: hydrogen; phenyl; tolyl; benzyl; alkoxyalkyl group having 1 to 10carbon atoms; hydroxyalkyl group having 1 to 10 carbon atoms;acyloxyalkyl group having 1 to 10 carbon atoms; a linear or branchedalkenyl group having 2 to 10 carbon atoms; and linear or branched alkyland fluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; and (c) a, a′, b, b′, and c, are integers, where aand a′ have a value of from 0 to 10, b and b′ have a value of 0 to 2with the proviso that sum of b and b′ is 1 or 2, and c has a value offrom 0 to
 20. 10. The process as set forth in claim 9 wherein saidcompound is derived from a hydroxy fatty acid selected from the groupconsisting of ricinoleic, lesquerolic, auricolic, and densipolic acid.11. The process as set forth in claim 9 wherein said compound is derivedfrom a non-drying oil selected from the group consisting of castor oiland lesquerella oil.
 12. The process as set forth in claim 8, whereinsaid ethylenically unsaturated carboxylic acid or its derivative has theformula:

wherein (a) R₉, R₁₀, and R₁₁, are the same or different and areindependently selected from the group consisting of: hydrogen; acarboxylate of the formula —COOR, where R is alkyl group having 1 to 10carbon atoms, or phenyl; phenyl; tolyl; benzyl; a linear or branchedalkenyl group having 2 to 10 carbon atoms; and linear or branched alkyland fluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; and (b) X is selected from the group consisting of:Br; Cl; hydroxy; alkoxy group having 1 to 4 carbon atoms; and acyloxygroup either derived from said ethylenically unsaturated carboxylic acidor having 2 to 4 carbon atoms.
 13. The process as set forth in claim 8wherein said ethylenically unsaturated ester has the formula:

wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same or differentand are each independently selected from the group consisting of:hydrogen; alkoxy group having 1 to 10 carbon atoms; alkoxyalkyl grouphaving 1 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y) where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (b) R₈ is selected from the group consisting of;—CN; —CH₂OR; —CONR′R″; and —CH₂NR′R″; where R, R′, and R″ are the sameor different and are independently selected from the group consistingof: hydrogen; phenyl; tolyl; benzyl; alkoxyalkyl group having 1 to 10carbon atoms; hydroxyalkyl group having 1 to 10 carbon atoms;acyloxyalkyl group having 1 to 10 carbon atoms; a linear or branchedalkenyl group having 2 to 10 carbon atoms; and linear or branched alkyland fluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1; (c) R₉, R₁₀,and R₁₁ are the same or different and are independently selected fromthe group consisting of: hydrogen; a carboxylate of the formula —COOR,where R is alkyl group having 1 to 10 carbon atoms, or phenyl; phenyl;tolyl; benzyl; a linear or branched alkenyl group having 2 to 10 carbonatoms; and linear or branched alkyl and fluoroalkyl groups having theformula C_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and (d) a, a′,b, b′, and c, are integers, where a and a′ have a value of from 0 to 10,b and b′ have a value of 0 to 2 with the proviso that sum of b and b′ is1 or 2, and c has a value of from 0 to
 20. 14. The process as set forthin claim 8 wherein the temperature is from about −10° C. to about 150°C. and the pressure is atmospheric.
 15. A product produced in accordancewith the process of claim 8.